Nitramines



United States Patent Ofiice 3,000,948 Patented Sept. 19, 1961 3,000,948 NITRAMINES Milton B. Frankel, Pasadena, and Karl Klager, Monrovia, Calif., assignors to Aerojet-General Corporation, Azusa, Califi, a corporation of Ohio No Drawing. Filed Feb. 19, 1957, Ser. No. 641,437 11 Claims. (Cl. 260-583) This invention relates to new compositions of matter useful as high explosives and a method for their preparation. In particular, this invention relates to nitramines having the general formula:

wherein A is an alkylene radical.

This application is a continuation-in-part of our copending application Serial No. 451,706, filed August 23, 1954, now abandoned.

The compounds of this invention are prepared by nitrating a secondary diamine, in accordance with the general reaction scheme set forth below:

wherein A is an alkylene radical.

The secondary diarnines used as starting materials in this invention are prepared by condensing a polynitro amine with 2,2,2-trinitroethano1, as disclosed in our copending application No. 451,705, filed August 23, 1954, now abandoned.

The nitration is effected in the conventional manner with nitric acid, however, We have found it desirable to employ a mixture of about equal amounts of nitric and sulfuric acid in order to hasten completion of the reaction.

To more clearly illustrate our invention, the following example is presented. It is to be understood, however, that this example is presented merely as a means of illustration, and is not intended to limit the scope of the in vention in any way.

EXAMPLE I Preparation of 1,1,I,3,6,6,8,10,I0,13,I5,15,15-tridecanitr3,8,13-triaza pentadecane In a flask fitted with a mechanical stirrer and thermometer, was placed 40 ml. of concentrated sulfuric acid and 40 ml. of 100% nitric acid. The mixture was cooled to 5 C. and 4 gm. of 1,1,l,6,6,8,l0,10,15,15,15- undecanitro-3,8,l3-triaza pentadecane was added. The mixture was warmed to a temperature of 30 C. for 1 hour, The mixture was then heated to a temperature of 4045 C. for a period of one-half hour. After cooling, a white solid precipitated which was collected, washed with water and dried. Recrystallization from nitromethanecarbon tetrachloride yielded 1,1,l,3,6,6,8, 10,10,13,15,15,15 tridecanitro 3,8,13 triaza pentadecane, m.p. 186-187 C, with decomposition. The elemental analysis of the product is as follows:

Calculated for C H N O percent C, 18.01; percent H, 2.02; percent N, 28.00. Found: percent C, 18.43;

percent H, 2.42; percent N, 27.85.

We have also found that secondary diarnines such as l,l,1,7,7,9,11,l1,17,17,17 undecanitro 3,9,15 triaza heptadecane, 1,1,1,8,8,l0,12,12,l9,19,19 undecanitro 3, 10,17-triaza nonadecane, and 1,1,1,9,9,11,13,13,21,21,21- undecanitro-3,l1,l9-triaza hemeicosane readily undergo nitration with nitric acid to form their corresponding nitrarnines, namely, l,l,1,3,7,7,9,11,1l,l5,l7,l7,l7-tridecanitro 3,9,15 triaza heptadecane, 1,l,l,3,8,8,10, l2,l2,17,19,19,l9 tridecanitro 3,10,17 triaza nonadecane, and l,l,l,3,9,9,ll,13,13,l9,2l,2l,2l-tridecanitro- 3,11,19-triaza hemeicosane.

From the discussion above, it is apparent that any member of this series of nitramines may be prepared simply by reacting an appropriate secondary diamine with nitric acid, in accordance with the teachings of this invention.

The new nitramines of our invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in United States Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives of this invention in a device such as that disclosed in United States Patent No. 2,470,162, is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is suificiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an imactor time fuse-mechanism firing a detonating explosive such as lead azide or mercury fulwherein A is a lower alkylene radical.

2. As a composition of matter, l,l,1,3,6,6,8,10,l0,13, 15,15,15-tridecanitro-3,8,l3-triaza pentadecane having the structural formula:

N0: N0: N0, 17w, N0: IP10] N02 NO2-C-CHT'N-CHiCHI--OHI-N-CHf-CHQOHI-N-CH2- %N O:

N02 N02 N05 N0 3. As a composition of matter, 1,1,1,3,7,7,9,l1,11,15,

17,17,17-tridecanitro-3,9,15-triaza heptadecane having the structural formula:

4. As a composition of matter, 1,1,1,3,8,8,10,l2,12,17, 19,19,19 tridecanitro 3,10,17 triaza nonadecane having the structural formula:

5. As a composition of matter, 1,l,1,3,9,9,l1,13,13,19,

3 21,21,21 tridecanitro 3,11,19 triaza hemeicosane having the structural formula:

which comprises nitrating a secondary diamine having the formula:

wherein A is a lower alkylene radical.

7. The method of claim 6 wherein the nitration is effected by a mixture of sulfuric and nitric acid.

8. The method of preparing 1,1,1,3,6,6,8,10,10,13,15, 15 ,15-tridecanitro-3,S,13-triaza pentadecane which comprises nitrating 1,1,1,6,6,8,10,10,15,15,15 undecanitro- 3,8,13-triaza pentadecane.

9. The method of preparing i,1,1,3,7,7,9,11,11,15,17, 17 ,17 tridecanitro-3,9,15-triaza heptadecane which comprises nitrating 1,1,1,7,7,9,11,l1,17,17,17 undecanitro- 3,9,15-triaza heptadeoane.

10. The method of preparing 1,1,1,3,8,8,10,12,12,17,19, 19,19 tridecanitro 3,10,17 triaza nonadecane which comprises nitrating 1,1,1,8,8,l0,12,12,19,19,19 undecanitro-3,10,17-triaza nonadeoane.

11. The method of preparing 1,1,1,3,9,9,11,13,13,19,21, 21,21 tridecanitro 3,11,19 triaza hemeicosane which comprises nitrating l,1,1,9,9,11,13,13,21,2l,21 -undecanitrc 3,11,19-triaza hemeicosane.

References Cited in the file of this patent Weygand: Organic Preparations, Interscience Pubfishers, Inc., N.Y., 1945, pp. 280-284. 

1. AS COMPOSITIONS OF MATTER, THE NITRAMINES HAVING THE FORMULA:
 6. THE METHOD OF PREPARING NITRAMINES HAVING THE FORMULA: 